The ignition dynamics of a CH₄: O₂: N₂: Ar = 1: 4: 15: 80 mixture by a high-voltage nanosecond discharge is simulated numerically with allowance for experimental data on the dynamics of the discharge current and discharge electric field. The calculated induction time agrees well with experimental data. It is shown that active particles produced in the discharge at a relatively low deposited energy can reduce the induction time by two orders of magnitude. Comparison of simulation results for mixtures with and without nitrogen shows that addition of nitrogen to the mixture leads to a decrease in the average electron energy in the discharge and gives rise to new mechanisms for accumulation of oxygen atoms due to the excitation of nitrogen electronic states and their subsequent quenching in collisions with oxygen molecules. Acceleration of the discharge-initiated ignition is caused by a faster initiation of chain reactions due to the production of active particles, first of all oxygen atoms, in the discharge.

Polycystic ovary syndrome (PCOS) is a complex disorder that impacts both the endocrine and metabolic systems, often resulting in infertility, obesity, insulin resistance, and cardiovascular complications. The aim of this study is to investigate the role of intestinal flora and its metabolites, particularly short-chain fatty acids (SCFAs), in the development of PCOS, and to assess the effects of metformin therapy on these components. SCFA levels in fecal and blood samples from women with PCOS ($n=69$) and healthy controls ($n=18$) were analyzed using Gas Chromatography–Mass Spectrometry (GC/MS) for precise measurement. Fecal microbiota were quantitatively detected by real-time polymerase chain reaction (PCR). To assess the efficacy of six months of metformin treatment, changes in the microbiota and SCFAs in the PCOS group ($n=69$) were also evaluated. The results revealed that women with PCOS exhibited a significant reduction in beneficial bacteria (namely, the C. leptum group and Prevotella spp.) alongside a notable overgrowth of opportunistic microorganisms (C. perfringens, C. difficile, Staphylococcus spp., and Streptococcus spp.). An overproduction of acetic acid (AA, $\mathrm{FC}=0.47$, $p<0.05$) and valeric acid (VA, $\mathrm{FC}=0.54$, $p<0.05$) suggests a link between elevated SCFAs and the development of obesity and PCOS. Interestingly, AA in the bloodstream might offer a protective effect against PCOS by ameliorating key symptoms such as high body mass index ($r=-0.33$, $p=0.02$), insulin resistance ($r=-0.39$, $p=0.02$), and chronic inflammation. Although serum SCFA levels showed non-significant changes following metformin treatment ($p>0.05$), the normalization of AA in the gut underscores that metformin exerts a more pronounced effect locally within the gastrointestinal tract. Furthermore, the study identified the most effective model for predicting the success of metformin therapy, based on serum concentrations of butyric acid (BA) and VA, achieving a 91% accuracy rate, 100% sensitivity, and 80% specificity. These promising findings highlight the potential for developing targeted interventions and personalized treatments, ultimately improving clinical outcomes for women with PCOS.

Here we report the observation that, depending on the solvent used for the electrospray, 2-nitrophloroglucinol undergoes a deprotonation from different sites forming two tautomeric gas phase ions. Those ions differ by the collision-induced dissociation (CID) spectra and by the gas phase hydrogen/deuterium (H/D) exchange kinetic. We performed H/D exchange in the electrospray ionization (ESI) source by saturation ESI region with vapors of deuterated solvent (D₂O). It was observed that [2-nitrophloroglucinol-H]⁻ exchanges two –OH hydrogens when MeOD is used as the spray solvent but when the spray solvent is 50:50 MeOD/D₂O we observed an additional two H/D exchanges at the aromatic ring. We propose that the reaction occurs via a keto–enol tautomerization mechanism which was found to be energetically favorable.

It has previously been reported that different conformations of oligonucleotides may be detected using a gas-phase hydrogen/deuterium (H/D) exchange performed in the collision cell of a mass spectrometer. The presence of different conformers was postulated based on the bimodal shape of the deuterium distribution and on the ion mobility spectrometry data. Here we implement an in-electrospray ionization source H/D exchange to detect the different conformations of oligonucleotides in the region of ion formation. We observed that the number of H/D exchanges depends considerably on the temperature of the desolvating capillary and varies from 25% at 50°C to 80% at 450°C, but no bimodality in the shape of the deuterium distribution was observed. Such results indicate that in the region of ion formation different conformations of oligonucleotide ions rapidly interconvert one into another.

Endometriosis is a prevalent chronic inflammatory disease characterized by a considerable delay between initial symptoms and diagnosis through surgery. The pressing need for a timely, non-invasive diagnostic solution underscores the focus of current research efforts. This study examines the diagnostic potential of the menstrual blood lipidome. The lipid profile of 39 samples (23 women with endometriosis and 16 patients in a control group) was acquired using reverse-phase high-performance liquid chromatography–mass spectrometry with LipidMatch processing and identification. Profiles were normalized based on total ion counts. Significant differences in lipids were determined using the Mann–Whitney test. Lipids for the diagnostic model, based on logistic regression, were selected using a combination of variance importance projection filters and Akaike information criteria. Levels of ceramides, sphingomyelins, cardiolipins, triacylglycerols, acyl- and alkenyl-phosphatidylethanolamines, and alkenyl-phosphatidylcholines increased, while acyl- and alkyl-phosphatidylcholines decreased in cases of endometriosis. Plasmenylphosphatidylethanolamine PE P-16:0/18:1 and cardiolipin CL 16:0_18:0_22:5_22:6 serve as marker lipids in the diagnostic model, exhibiting a sensitivity of 81% and specificity of 85%. The diagnostic approach based on dried spots of menstrual blood holds promise as an alternative to traditional non-invasive methods for endometriosis screening.